JP2006257048A - Borate-containing polymerizable (meth)acrylate - Google Patents
Borate-containing polymerizable (meth)acrylate Download PDFInfo
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本発明は、新規なホウ酸塩基含有重合性(メタ)アクリレートに関するものであり、特にホウ酸塩基を有する水溶性又は水膨潤性ポリマーの原料として有用である。 The present invention relates to a novel borate group-containing polymerizable (meth) acrylate, and is particularly useful as a raw material for a water-soluble or water-swellable polymer having a borate group.
モノアミン、ジアミンなどのアミン化合物とホウ酸との反応生成物は古くから研究されている（特許文献１および２参照）。これらの文献では、アミン化合物とホウ酸とを反応させて得られる水溶液を、そのままラテックスの凝固剤あるいはα-アルキルアクロレインの製造用触媒として用いている。しかしながら、ホウ酸塩基を含有した重合性(メタ)アクリル系モノマーについては知られていない。 Reaction products of amine compounds such as monoamine and diamine and boric acid have been studied for a long time (see Patent Documents 1 and 2). In these documents, an aqueous solution obtained by reacting an amine compound and boric acid is used as it is as a latex coagulant or a catalyst for producing α-alkylacrolein. However, a polymerizable (meth) acrylic monomer containing a borate group is not known.
本発明の目的は、新規な重合性のホウ酸塩基含有(メタ)アクリレートモノマーを提供することにある。 An object of the present invention is to provide a novel polymerizable borate group-containing (meth) acrylate monomer.
本発明者は、前記目的を達成すべく、鋭意検討を重ねた結果、アミノ基含有(メタ)アクリレートと安価なホウ酸とを反応して、(メタ)アクリレートの二重結合が保持されたままホウ酸塩基を導入することに成功し、本発明を完成するに至った。
即ち、本発明は、(A)アミノ基含有(メタ)アクリレートのアミノ基に(B)無機ホウ酸系化合物が結合してなり、アミノ基1個当たりホウ素原子を1〜8個含有してなるホウ酸塩基含有重合性(メタ)アクリレートを提供する。
As a result of intensive studies to achieve the above object, the present inventor reacted amino group-containing (meth) acrylate with inexpensive boric acid, and the double bond of (meth) acrylate was retained. Successful introduction of borate group has led to the completion of the present invention.
That is, the present invention comprises (A) an amino group of (A) amino group-containing (meth) acrylate and (B) an inorganic boric acid compound bonded thereto, and contains 1 to 8 boron atoms per amino group. A borate group-containing polymerizable (meth) acrylate is provided.
本発明のホウ酸塩基含有(メタ)アクリレートは、分子中にホウ酸塩基を有することにより
生体適合性の高いポリマー又はゲルの合成に有効なモノマーとして用いられる。
The borate group-containing (meth) acrylate of the present invention has a borate group in the molecule, so that it is used as a monomer effective for the synthesis of a polymer or gel having high biocompatibility.
本発明においてアミノ基含有(メタ)アクリレートとしては、一般式(1)
また、本発明においてアミノ基含有アクリレートの他の具体例としては、ジメチルアミノプロピルアクリルアミド、7-アミノ-3,7-ジメチルオクチルアクリレートなどが挙げられる。
なお、本発明で「(メタ)アクリレート」の表示は「アクリレート及び／又はメタクリレート」を意味する。
As the amino group-containing (meth) acrylate in the present invention, the general formula (1)
In the present invention, other specific examples of amino group-containing acrylates include dimethylaminopropylacrylamide, 7-amino-3,7-dimethyloctyl acrylate, and the like.
In the present invention, the expression “(meth) acrylate” means “acrylate and / or methacrylate”.
本発明での無機ホウ酸系化合物としては、一般式(2)
Ｂ（ＯＲ）ｎ（ＯＨ）３−ｎ (2)
(式中、ｎは0〜3までの整数、RはＣｍＨ2ｍ+1のアルキル基であり、ｍは1〜10の整数を表す。)で表わされるホウ酸およびホウ酸エステルが用いられる。ホウ酸の具体的なものとしては、例えばオルトホウ酸、メタホウ酸、四ホウ酸、およびそれらの混合物であり、また、ホウ酸エステルの具体的なものとしては、例えばホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル等が挙げられる。これらのホウ酸及びホウ酸エステルは、単独又は２種以上組み合わせて使用できる。上記の中ではホウ酸が最も好ましく用いられる。
As the inorganic boric acid compound in the present invention, the general formula (2)
B (OR) n (OH) 3-n (2)
(Wherein, n an integer from 0 to 3, R is an alkyl group C m H 2m + 1, m represents. An integer of 1 to 10) of boric acid and boric acid esters represented by used . Specific examples of boric acid include orthoboric acid, metaboric acid, tetraboric acid, and mixtures thereof, and specific examples of boric acid esters include trimethyl borate, triethyl borate, Examples include tripropyl borate and tributyl borate. These boric acid and boric acid ester can be used individually or in combination of 2 or more types. Of these, boric acid is most preferably used.
上記一般式で表されるアミノ基含有(メタ)アクリレートとホウ酸系化合物との反応によって得られるホウ酸塩基含有(メタ)アクリレート((メタ)アクリレートホウ酸塩)の具体例としては、ジメチルアミノエチルメタクリレートホウ酸塩、ジエチルアミノエチルメタクリレートホウ酸塩、ジメチルアミノエチルアクリレートホウ酸塩、ジメチルアミノプロピルアクリルアミドホウ酸塩などが挙げられる。N-アルキル置換アミノ(メタ)アクリレートの場合、結晶性の(メタ)アクリレートホウ酸塩が得られる。これに対して、N-アルキル置換アクリルアミド、例えばジメチルアミノプロピルアクリルアミドの場合、非結晶性のアクリレートホウ酸塩が得られる。これらの結晶性と非結晶の(メタ)アクリレートホウ酸塩のいずれも、ホウ素含有量の測定値が単核ホウ酸塩のホウ素含有量の計算値より高いことから、得られた(メタ)アクリレートホウ酸塩が多核縮合ホウ酸塩又は多核縮合ホウ酸塩を含有するものであると推定された。 Specific examples of the borate group-containing (meth) acrylate ((meth) acrylate borate) obtained by the reaction of the amino group-containing (meth) acrylate represented by the above general formula with a boric acid compound include dimethylamino Examples thereof include ethyl methacrylate borate, diethylaminoethyl methacrylate borate, dimethylaminoethyl acrylate borate, and dimethylaminopropyl acrylamide borate. In the case of N-alkyl substituted amino (meth) acrylates, crystalline (meth) acrylate borate is obtained. In contrast, in the case of N-alkyl substituted acrylamides such as dimethylaminopropyl acrylamide, amorphous acrylate borates are obtained. Both these crystalline and amorphous (meth) acrylate borates were obtained because the measured boron content was higher than the calculated boron content of the mononuclear borate. It was estimated that the borate contained polynuclear condensed borate or polynuclear condensed borate.
本発明におけるホウ酸塩基含有(メタ)アクリレートの合成は、例えば次のようにして行うことができる。即ち、溶媒にホウ酸を溶解させて攪拌しながら、アミノ基含有(メタ)アクリレートを滴下する。場合によっては、添加順序を逆にしてアミノ基含有(メタ)アクリレート溶液を攪拌しながら、それにホウ酸溶液を滴下する場合も可能である。続いて、室温または加熱下、一定時間保持叉は攪拌して、アミノ基含有(メタ)アクリレートとホウ酸の反応を行う。これによりホウ酸塩基含有(メタ)アクリレートが析出し、吸引濾過により沈殿物(ホウ酸塩基含有（メタ）アクリレート）を回収する。一方、反応生成物が反応溶媒に溶けている場合があり、その場合はエパポレーターにより溶媒を留去してホウ酸塩基含有(メタ)アクリレートを回収する。以上のようにして得られた反応生成物をN,N-ジメチルホルムアミド、アセトンなどを用いて数回繰り返し洗浄した後、真空乾燥することにより白色粉末の(メタ)アクリレートホウ酸塩が得られる。 The synthesis of the borate group-containing (meth) acrylate in the present invention can be performed, for example, as follows. That is, the amino group-containing (meth) acrylate is dropped while dissolving boric acid in a solvent and stirring. In some cases, it is possible to add the boric acid solution dropwise to the amino group-containing (meth) acrylate solution while stirring the amino group-containing (meth) acrylate solution. Subsequently, the reaction of amino group-containing (meth) acrylate and boric acid is carried out at room temperature or under heating for a certain period of time or stirring. Thereby, borate group-containing (meth) acrylate is precipitated, and the precipitate (borate group-containing (meth) acrylate) is recovered by suction filtration. On the other hand, the reaction product may be dissolved in the reaction solvent. In that case, the solvent is distilled off by an evaporator to recover the borate group-containing (meth) acrylate. The reaction product obtained as described above is washed several times with N, N-dimethylformamide, acetone or the like and then vacuum dried to obtain a white powder of (meth) acrylate borate.
本発明におけるホウ酸塩基含有アミノ基含有(メタ)アクリレートの合成溶媒としては、ホウ酸系化合物またはアミノ基含有(メタ)アクリレートの少なくとも一種を溶解するようなものが必要である。具体的には、例えば、メタノール、エタノール、イソプロパノールなどの低級アルコール、アセトン、メチルエチルケトン、テトラヒドロフラン、N,N-ジメチルホルムアミド、N-メチルピロリドン、N,N-ジメチルアセトアミド、ジメチルスルホキシド、水などが挙げられ、これらは単独又は二種以上の混合で使用できる。その中では、特にN,N-ジメチルホルムアミドを用いることが好ましい。溶媒の使用量は、ホウ酸系化合物およびアミノ基含有(メタ)アクリレートの合計100質量部に対して溶媒が300〜1500質量部となるように用いることが好ましい。 The boric acid group-containing amino group-containing (meth) acrylate synthesis solvent in the present invention is required to dissolve at least one of boric acid compounds or amino group-containing (meth) acrylates. Specific examples include lower alcohols such as methanol, ethanol and isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, water and the like. These can be used alone or in a mixture of two or more. Among them, it is particularly preferable to use N, N-dimethylformamide. The amount of the solvent used is preferably such that the solvent is 300 to 1500 parts by mass with respect to 100 parts by mass in total of the boric acid compound and the amino group-containing (meth) acrylate.
本発明におけるホウ酸塩基含有(メタ)アクリレートの合成条件として、アミノ基含有(メタ)アクリレートの中のアミノ基とホウ酸系化合物のホウ素とのモル比が重要である。ホウ酸系化合物の比率を増やすと、多核縮合ホウ酸塩が形成しやすく、高い収率でホウ酸塩基含有(メタ)アクリレートが得られる。一般的にアミノ基含有(メタ)アクリレートの中のアミノ基１モルに対して、ホウ素が０．1〜１０モルが好ましく、より好ましくは０．５〜８モル、特に好ましくは１〜６モルである。０．1モル未満又は１０モルを超える場合、(メタ)アクリレートホウ酸塩の収率が低くなり、得られる効果が小さくなる。また、反応温度について、用いるアミノ基含有(メタ)アクリレートの種類によっては異なるが、一般的に１５℃〜１５０℃が好ましく、より好ましくは２０℃〜１２０℃であり、特に好ましくは２５℃〜１００℃である。反応時間は反応温度にもよるが、通常１〜１５時間が好ましく用いられる。 As a synthesis condition of the borate group-containing (meth) acrylate in the present invention, the molar ratio of the amino group in the amino group-containing (meth) acrylate and boron of the boric acid compound is important. When the ratio of the boric acid compound is increased, a polynuclear condensed borate is easily formed, and a borate group-containing (meth) acrylate is obtained with a high yield. In general, 0.1 to 10 mol of boron is preferable, more preferably 0.5 to 8 mol, and particularly preferably 1 to 6 mol with respect to 1 mol of amino group in amino group-containing (meth) acrylate. is there. When it is less than 0.1 mol or more than 10 mol, the yield of (meth) acrylate borate becomes low, and the obtained effect becomes small. The reaction temperature varies depending on the type of amino group-containing (meth) acrylate to be used, but is generally preferably 15 ° C to 150 ° C, more preferably 20 ° C to 120 ° C, and particularly preferably 25 ° C to 100 ° C. ° C. The reaction time depends on the reaction temperature, but usually 1 to 15 hours is preferably used.
本発明のホウ酸塩基含有(メタ)アクリレートは、アミノ基1個当たりホウ素原子を１〜８個含有しており、アミン特有の刺激臭が殆どない固形状粉末であり、水またはメタノールなどの低級アルコールによく溶ける性質を持っており、重合用モノマーとして好適に用いられる。
本発明のホウ酸塩基含有(メタ)アクリレートは、それ単独で重合するか、又は他のビニルモノマーと共重合することができる。
The borate group-containing (meth) acrylate of the present invention contains 1 to 8 boron atoms per amino group and is a solid powder having almost no irritating odor peculiar to amines. It has a property of being well soluble in alcohol and is suitably used as a monomer for polymerization.
The borate group-containing (meth) acrylates of the present invention can be polymerized alone or copolymerized with other vinyl monomers.
本発明を次の実施例によって更に具体的に説明する。尚、例中の％は特に断らない限り重量基準である。
(実施例1) [ジメチルアミノエチルメタクリレート縮合ホウ酸塩の合成]
ホウ酸20g(0.324mol)をDMF 100gに溶かした溶液を攪拌しながら、ジメチルアミノエチルメタクリレート50.9g(0.324mol)を滴下した。白色沈殿が徐々に析出した。室温で15時間攪拌して、吸引濾過により沈殿物を回収した。続いて、得た沈殿物をアセトンで二回洗浄し、50℃、2時間真空乾燥したところ、原料に対して23.9%の収率で反応生成物の白色粉末1a 16.9gを得た。また、濾液をエパポレーターでDMFを留去し、得た白色固体をアセトンで二回洗った。50℃、2時間真空乾燥により、原料に対して9.4%の収率で1aと同一の反応生成物の白色粉末6.7gを得た。分析結果は表1〜3に示す。
The invention is further illustrated by the following examples. In the examples, “%” is based on weight unless otherwise specified.
(Example 1) [Synthesis of dimethylaminoethyl methacrylate condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 100 g of DMF, 50.9 g (0.324 mol) of dimethylaminoethyl methacrylate was added dropwise. A white precipitate gradually precipitated. The mixture was stirred at room temperature for 15 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed twice with acetone and vacuum dried at 50 ° C. for 2 hours. As a result, 16.9 g of white powder 1a as a reaction product was obtained in a yield of 23.9% based on the raw material. Further, DMF was distilled off from the filtrate with an evaporator, and the obtained white solid was washed twice with acetone. By vacuum drying at 50 ° C. for 2 hours, 6.7 g of a white powder of the same reaction product as 1a was obtained in a yield of 9.4% based on the raw material. The analysis results are shown in Tables 1-3.
(実施例2) [ジメチルアミノエチルメタクリレート縮合ホウ酸塩の合成]
ホウ酸20g(0.324mol)をDMF 100gに溶かした溶液を攪拌しながら、ジメチルアミノエチルメタクリレート25.5g(0.162mol)を滴下した。白色沈殿が徐々に析出した。室温で8時間攪拌して、吸引濾過により沈殿物を回収した。続いて、得た沈殿物をアセトンで二回洗浄し、70℃、4時間真空乾燥したところ、原料に対して39.7%の収率で1aと同一の反応生成物の白色粉末16.7gを得た。
(Example 2) [Synthesis of dimethylaminoethyl methacrylate condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 100 g of DMF, 25.5 g (0.162 mol) of dimethylaminoethyl methacrylate was added dropwise. A white precipitate gradually precipitated. The mixture was stirred at room temperature for 8 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed twice with acetone and vacuum-dried at 70 ° C. for 4 hours to obtain 16.7 g of a white powder of the same reaction product as 1a in a yield of 39.7% with respect to the raw material. .
(実施例3) [ジエチルアミノエチルメタクリレート縮合ホウ酸塩の合成]
ホウ酸20g(0.324mol)をDMF 100gに溶かした溶液を攪拌しながら、ジエチルアミノエチルメタクリレート25.5g(0.162mol)を滴下し、室温で19時間攪拌した。得られた溶液をエパポレーターでDMFを留去した後、70℃、2時間真空乾燥した。続いて、得た白色固体をアセトンで３回洗浄し、70℃、2時間真空乾燥したところ、原料に対して54.7%の収率で反応生成物の白色粉末1b 27.4gを得た。分析結果は表1〜3に示す。
(Example 3) [Synthesis of diethylaminoethyl methacrylate condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 100 g of DMF, 25.5 g (0.162 mol) of diethylaminoethyl methacrylate was added dropwise and stirred at room temperature for 19 hours. After distilling off DMF with an evaporator, the obtained solution was vacuum dried at 70 ° C. for 2 hours. Subsequently, the obtained white solid was washed with acetone three times and vacuum dried at 70 ° C. for 2 hours to obtain 27.4 g of white powder 1b as a reaction product in a yield of 54.7% with respect to the raw material. The analysis results are shown in Tables 1-3.
(実施例4) [ジメチルアミノエチルアクリレート縮合ホウ酸塩の合成]
ホウ酸20g(0.324mol)をDMF 100gに溶かした溶液を攪拌しながら、ジメチルアミノエチルアクリレート23.2g(0.162mol)を滴下した。白色沈殿が析出した。室温で15時間攪拌して、吸引濾過により沈殿物を回収した。続いて、得た沈殿物をアセトンで二回洗浄し、50℃、4時間真空乾燥したところ、原料に対して49.1%の収率で反応生成物の白色粉末1c 21.2gを得た。また、濾液をエパポレーターでDMFを留去し、得た白色固体をアセトンで二回洗った。50℃、2時間真空乾燥により、原料に対して5%の収率で反応生成物の白色粉末2c 2.1gを得た。分析結果は表1〜3に示す。
(Example 4) [Synthesis of dimethylaminoethyl acrylate condensed borate]
While stirring a solution of 20 g (0.324 mol) boric acid in 100 g DMF, 23.2 g (0.162 mol) dimethylaminoethyl acrylate was added dropwise. A white precipitate was deposited. The mixture was stirred at room temperature for 15 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed twice with acetone and vacuum-dried at 50 ° C. for 4 hours to obtain 21.2 g of a white powder 1c of the reaction product in a yield of 49.1% with respect to the raw material. Further, DMF was distilled off from the filtrate with an evaporator, and the obtained white solid was washed twice with acetone. By vacuum drying at 50 ° C. for 2 hours, 2.1 g of white powder 2c of the reaction product was obtained with a yield of 5% based on the raw material. The analysis results are shown in Tables 1-3.
(実施例5) [ジメチルアミノプロピルアクリルアミド縮合ホウ酸塩の合成]
ホウ酸20g(0.324mol)をDMF 100gに溶かした溶液を攪拌しながら、ジメチルアミノプロピルアクリルアミド25.3g(0.162mol)を滴下し、室温で15時間攪拌した。少量の白色沈殿を生じた溶液をエパポレーターでDMFを留去した後、アセトンで３回洗浄した。引き続き、70℃、2時間真空乾燥することにより原料に対して58.4%の収率で反応生成物の白色粉末1d 26.5gを得た。分析結果は表1〜3に示す。
(Example 5) [Synthesis of dimethylaminopropylacrylamide condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 100 g of DMF, 25.3 g (0.162 mol) of dimethylaminopropylacrylamide was added dropwise and stirred at room temperature for 15 hours. The solution in which a small amount of white precipitate was formed was evaporated with an evaporator and then washed with acetone three times. Subsequently, vacuum drying was performed at 70 ° C. for 2 hours to obtain 26.5 g of white powder 1d as a reaction product in a yield of 58.4% with respect to the raw material. The analysis results are shown in Tables 1-3.
尚、表中及び本文中の略号は次の化合物を示す。
DMAEM: N,N-ジメチルアミノエチルメタクリレート
DEAEM: N,N-ジエチルアミノエチルメタクリレート
DMAEA: N,N-ジメチルアミノエチルアクリレート
DMAPAA: N,N-ジメチルアミノプロピルアクリルアミド
DMAA: N,N-ジメチルアクリルアミド
VA-086: 2,2'-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド]
AIBN: アゾビスイソブチロニトリル
In addition, the symbol in a table | surface and the text shows the following compound.
DMAEM: N, N-dimethylaminoethyl methacrylate
DEAEM: N, N-diethylaminoethyl methacrylate
DMAEA: N, N-dimethylaminoethyl acrylate
DMAPAA: N, N-dimethylaminopropylacrylamide
DMAA: N, N-dimethylacrylamide
VA-086: 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]
AIBN: Azobisisobutyronitrile
(応用例１)
DMAEMホウ酸塩2g、ラジカル開始剤VA-086の10%水溶液73mgを脱酸素水20gに加え、溶解させた。次に20分窒素バップリングして、窒素雰囲気下、90℃、7時間で重合を行った。得られたポリマー溶液はエパポレーターで溶媒を留去した後、アセトンで二回洗浄を行い、更に真空乾燥した。得られたポリマーの収率は90%である。また、ホウ素含有率はプラズマ発光分析によって１６％であった。
(Application 1)
2 g of DMAEM borate and 73 mg of a 10% aqueous solution of radical initiator VA-086 were added to 20 g of deoxygenated water and dissolved. Next, nitrogen bubbling was performed for 20 minutes, and polymerization was performed in a nitrogen atmosphere at 90 ° C. for 7 hours. The obtained polymer solution was evaporated twice with an evaporator, then washed twice with acetone, and further vacuum-dried. The yield of the obtained polymer is 90%. The boron content was 16% by plasma emission analysis.
Claims (3)
3. The borate group-containing polymerizable (meth) acrylate according to claim 1, wherein the inorganic boric acid compound is boric acid or a borate ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005079228A JP2006257048A (en) | 2005-03-18 | 2005-03-18 | Borate-containing polymerizable (meth)acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005079228A JP2006257048A (en) | 2005-03-18 | 2005-03-18 | Borate-containing polymerizable (meth)acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006257048A true JP2006257048A (en) | 2006-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2005079228A Pending JP2006257048A (en) | 2005-03-18 | 2005-03-18 | Borate-containing polymerizable (meth)acrylate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9095141B2 (en) | 2012-07-31 | 2015-08-04 | Empire Technology Development Llc | Antifouling compositions including dioxaborinanes and uses thereof |
| US9290598B2 (en) | 2012-03-29 | 2016-03-22 | Empire Technology Development Llc | Dioxaborinane co-polymers and uses thereof |
| US9352485B2 (en) | 2012-03-23 | 2016-05-31 | Empire Technology Development Llc | Dioxaborinanes and uses thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59232199A (en) * | 1983-06-16 | 1984-12-26 | 花王株式会社 | Detergent composition for machines |
| JPS6211799A (en) * | 1985-07-10 | 1987-01-20 | Yushiro Do Brazil Ind Chem Ltd | Cold rolling oil composition |
| JP2000143673A (en) * | 1998-09-08 | 2000-05-26 | Hokko Chem Ind Co Ltd | Triarylborane-amine compound, triarylborane-amine- based (co)polymer and underwater antifouling agent containing the same as active ingredient |
-
2005
- 2005-03-18 JP JP2005079228A patent/JP2006257048A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59232199A (en) * | 1983-06-16 | 1984-12-26 | 花王株式会社 | Detergent composition for machines |
| JPS6211799A (en) * | 1985-07-10 | 1987-01-20 | Yushiro Do Brazil Ind Chem Ltd | Cold rolling oil composition |
| JP2000143673A (en) * | 1998-09-08 | 2000-05-26 | Hokko Chem Ind Co Ltd | Triarylborane-amine compound, triarylborane-amine- based (co)polymer and underwater antifouling agent containing the same as active ingredient |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9352485B2 (en) | 2012-03-23 | 2016-05-31 | Empire Technology Development Llc | Dioxaborinanes and uses thereof |
| US9290598B2 (en) | 2012-03-29 | 2016-03-22 | Empire Technology Development Llc | Dioxaborinane co-polymers and uses thereof |
| US9095141B2 (en) | 2012-07-31 | 2015-08-04 | Empire Technology Development Llc | Antifouling compositions including dioxaborinanes and uses thereof |
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